TWI810371B - Curable composition, hardened product, and method of using the curable composition - Google Patents

Abstract

The present invention provides a curable composition characterized by comprising: the following components (A) and (E); a cured product obtained by curing the curable composition; A method of using the composition as an adhesive for an optical element fixing material or a sealing material for an optical element fixing material. The curable composition of the present invention is excellent in curability and has a low refractive index. (A) Component: It is a curable polysilsesquioxane compound (polysilsesquioxane) having a repeating unit represented by the following formula (a-1), which satisfies the specific conditions for ²⁹ Si-NMR, and the mass average molecular weight (Mw) For a specific range of hardening polysilsesquioxane compounds, [R ¹ is a fluoroalkyl group represented by the compositional formula: C _m H _(2m-n+1) F _n . m represents an integer of 1 to 10, and n represents an integer of not less than 2 and not more than (2m+1). D represents the linking group (except for the alkylene group) or the single bond that ^R1 and Si are bonded to] (E) Component: It is a fine particle with an average primary particle diameter of more than 0.04 μm and 8 μm or less.

Description

Curing composition, cured product and method of using the curable composition

The present invention relates to a curable composition with good curability and low refractive index, a cured product obtained by curing the curable composition with high adhesive strength, and the use of the curable composition as an optical element fixing material How to use adhesives or sealing materials for optical element fixing materials.

Conventionally, curable compositions have been improved in various ways according to their applications, and have been widely used industrially as raw materials for optical components and molded articles, adhesives, coating agents, and the like. In addition, curable compositions are also attracting attention as compositions for optical element fixing materials such as adhesives for optical element fixing materials and sealing materials for optical element fixing materials.

Optical elements are various lasers such as semiconductor lasers (LD), light-emitting elements such as light-emitting diodes (LED), light-receiving elements, composite optical elements, and optical integrated circuits. In recent years, optical devices that emit blue light or white light with shorter wavefront wavelengths have been developed and widely used. Such a light-emitting element with a short wavefront wavelength is rapidly increasing in luminance, and the amount of heat generated by the optical element tends to increase further.

On the other hand, in recent years, along with the high brightness of optical elements, the cured product of the optical element fixing material composition is exposed to higher energy light and higher temperature heat generated by optical elements for a long time, resulting in Then the problem of low power.

In order to solve this problem, in Patent Documents 1 to 3, a composition for an optical element fixing material containing a polysilsesquioxane compound as a main component is proposed. However, even in the cured products of the compositions described in Patent Documents 1 to 3, it may be difficult to obtain heat resistance while maintaining sufficient adhesive force.

In addition, when using a curable composition to fix an optical element or the like, it is often important to form a cured product having a refractive index suitable for the purpose. In particular, since many cured products of conventional curable compositions have a high refractive index, curable compositions with lower refractive indices have been demanded.

Patent Document 4 describes a curable composition containing a curable polysilsesquioxane compound having a fluoroalkyl group as a curable composition for supplying a cured product having a low refractive index. However, as shown in the Examples of Patent Document 4, when a curable composition containing a curable polysilsesquioxane compound having a high ratio of repeating units having a fluoroalkyl group is used, it is difficult to obtain a cured composition with high adhesive strength. thing. Thus, the cured product of the curable composition described in Patent Document 4 has a difficult relationship between high adhesive strength and low refractive index. Therefore, when the curable composition described in Patent Document 4 is used, it is difficult to obtain a cured product having both high adhesive strength and low refractive index.

In addition, it is known to add fillers and the like to curable compositions to improve workability and the like. However, in general, since cured compositions containing fillers and the like tend to have a high refractive index, cured compositions are desired to have a low refractive index even when fillers and the like are added. [Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2004-359933 Patent Document 2: Japanese Patent Laid-Open No. 2005-263869 Patent Document 3: Japanese Patent Laid-Open No. 2006-328231 Patent Document 4: WO2017/110948 (US2018/0355111 A1)

[Problem to be solved by the invention]

The present invention has been accomplished in view of the above-mentioned conventional technology, and its object is to provide a curable composition with good curability and a low refractive index, and a curable composition with high adhesive strength obtained by curing the curable composition. and a method of using the curable composition as an adhesive for an optical element fixing material or a sealing material for an optical element fixing material. In the present invention, the "curable composition" refers to a composition that is transformed into a cured product by satisfying specific conditions such as heating. [means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive studies on curable polysilsesquioxane compounds having a fluoroalkyl group. As a result, it was found that (1) The so-called problem that the adhesive strength of the cured product is lowered due to the introduction of fluoroalkyl groups into the curable polysilsesquioxane compound can be solved by using a compound that has a specific repeating unit and satisfies the conditions regarding the molecular structure ( The following condition 1), and the curable polysilsesquioxane compound (hereinafter, sometimes referred to as "curable polysilsesquioxane compound (A)") of the molecular weight condition (the following condition 2) solve, and (2) Since the curable composition containing the curable polysilsesquioxane compound (A) has good curability properties, it also has the advantage of being able to undergo a curing reaction without excessive heating. Furthermore, by using a curable composition containing a curable polysilsesquioxane compound (A) and fine particles having an average primary particle diameter exceeding 0.04 μm and 8 μm or less, a cured product having excellent peeling resistance can be formed. The present invention has been accomplished based on such knowledge.

Therefore, according to the present invention, there are provided curable compositions of the following [1] to [8], cured products of [9] and [10], and methods of using the curable compositions of [11] and [12].

[1] A curable composition comprising the following components (A) and (E), Component (A): It is a curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1), and is a curable polysilsesquioxane compound that satisfies the following conditions 1 and 2 ,

[chemical 1]

[R ¹ is a fluoroalkyl group represented by the compositional formula: C _m H _(2m-n+1) F _n . m represents an integer of 1 to 10, and n represents an integer of not less than 2 and not more than (2m+1). D represents a linking group (except for an alkylene group) or a single bond that ^R1 and Si are bonded to] [Condition 1] When ²⁹ Si-NMR of a hardening polysilsesquioxane compound is measured, no In the area full of -52ppm [area (2)], 1 or more peaks were observed, in the area above -52ppm and less than -45ppm [district city (1)] and the area of -73ppm and less than -62ppm[ In at least one of the regions (3)], 1 or more peaks were observed, and Z2 derived from the following formula was 20 to 40%.

[number 1]

P1: Integral value in area (1) P2: Integral value in area (2) P3: Integral value in area (3) [Condition 2] The mass average molecular weight (Mw) of hardening polysilsesquioxane compound is 4,000~11,000, Component (E): Fine particles having an average primary particle diameter of more than 0.04 μm and not more than 8 μm. [2] The curable composition as described in [1], wherein the proportion of the repeating unit represented by the formula (a-1) as the above-mentioned curable polysilsesquioxane compound is 25 mol with respect to the total repeating units % or more. [3] The curable composition according to [1] or [2], wherein the curable polysilsesquioxane compound further has a repeating unit represented by the following formula (a-2).

[Chem 2]

[R ² represents an unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms] [4] The curable composition as described in [3], Here, the ratio of the repeating unit represented by the formula (a-2) of the curable polysilsesquioxane compound is more than 0 mol% and not more than 75 mol% with respect to the total repeating units. [5] The curable composition according to any one of [1] to [4], wherein when ^{the 29} Si-NMR of the curable polysilsesquioxane compound is measured, in the region (3) , 1 or more peaks were observed, and Z3 derived from the following formula was 60 to 80%.

[number 2]

[6] The curable composition according to any one of [1] to [5], which further contains the following component (B), (B) Component: a silane coupling agent with nitrogen atoms in the molecule. [7] The curable composition according to any one of [1] to [6], which further contains the following component (C), (C) Component: A silane coupling agent with an acid anhydride structure in the molecule. [8] The curable composition according to any one of [1] to [7], which further contains the following component (D), (D) Component: Microparticles with an average primary particle diameter of 5 to 40 nm. [9] A cured product obtained by curing the curable composition described in any one of [1] to [8] above. [10] The cured product described in [9], which is an optical element fixing material. [11] A method of using a curable composition, using the curable composition described in any one of [1] to [8] above as an adhesive for an optical element fixing material. [12] A method of using a curable composition, using the curable composition described in any one of [1] to [8] above as a sealing material for an optical element fixing material. [Effect of the invention]

According to the present invention, there are provided a curable composition having good curability and a low refractive index, a cured product obtained by curing the curable composition, and a cured product having high adhesive strength, and the curable composition as an optical device. How to use an adhesive for fixing materials or a sealing material for optical element fixing materials.

Hereinafter, the present invention will be divided into 1) a curable composition, 2) a cured product, and 3) a method of using the curable composition and will be described in detail.

1) Hardening composition The curable composition of the present invention is characterized in that it contains the following (A) component and (E) component, Component (A): It is a curable polysilsesquioxane compound having a repeating unit represented by the above-mentioned formula (a-1), and is a curable polysilsesquioxane compound satisfying the above-mentioned condition 1 and condition 2 [hardenable polysilsesquioxane compound] Sexual polysilsesquioxane compound (A)], Component (E): Fine particles having an average primary particle diameter of more than 0.04 μm and not more than 8 μm. In addition, in the present invention, the term "curable polysilsesquioxane compound" refers to a polysilsesquioxane compound that is independently converted into a cured product by satisfying specific conditions such as heating, or, in A polysilsesquioxane compound that functions as a curable component in the above curable composition.

[(A) ingredient] Component (A) constituting the curable composition of the present invention is a curable polysilsesquioxane compound having a repeating unit represented by the following formula (a-1), and is a curable polysilsesquioxane compound that satisfies the above-mentioned conditions 1 and 2. Non-toxic polysilsesquioxane compounds.

[Chem 3]

[R ¹ is a fluoroalkyl group represented by the compositional formula: C _m H _(2m-n+1) F _n . m represents an integer of 1 to 10, and n represents an integer of not less than 2 and not more than (2m+1). D represents a linking group (but excluding an alkylene group) or a single bond] to which R ¹ is bonded to Si.

In the formula (a-1), R ¹ is a fluoroalkyl group represented by the composition formula: C _m H _(2m-n+1) F _n . m represents an integer of 1 to 10, and n represents an integer of not less than 2 and not more than (2m+1). m is preferably an integer of 1-5, more preferably an integer of 1-3. By using a curable polysilsesquioxane compound having R ¹ , a curable composition with a low refractive index can be obtained.

Examples of the fluoroalkyl group represented by the composition formula: C _m H _(2m-n+1) F _n include CF ₃ , CF ₃ CF ₂ , CF ₃ (CF ₂ ) ₂ , CF ₃ (CF ₂ ) ₃ , CF ₃ (CF ₂ ) ₄ , CF ₃ (CF ₂ ) ₅ , CF ₃ (CF ₂ ) ₆ , CF ₃ (CF ₂ ) ₇ , CF ₃ (CF ₂ ) ₈ , CF ₃ (CF ₂ ) _{9 etc.} Alkyl; CF ₃ CH ₂ CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ and other hydrofluoroalkanes base.

In the formula (a-1), D represents a linking group (however, excluding an alkylene group) or a single bond to which R ¹ is bonded to Si. Examples of the linking group for D include C6-20 arylene groups such as 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, and 1,5-naphthylene. Aryl.

The curable polysilsesquioxane compound (A) may have one type (R ¹ -D) (homopolymer), or may have two or more types (R ¹ -D) (copolymer). When the hardening polysilsesquioxane compound (A) is a copolymer, the hardening polysilsesquioxane compound (A) may be a random copolymer, a block copolymer, a grafting copolymer (grafting copolymer), an interactive Any of copolymers and the like, but random copolymers are preferable from the viewpoint of easiness of manufacture. In addition, the structure of the curable polysilsesquioxane compound (A) may be any of a stepped structure, a double-layer structure, a cage structure, a partially split cage structure, a ring structure, and a random structure. a structure.

The proportion of the repeating unit represented by the formula (a-1) contained in the curable polysilsesquioxane compound (A) is preferably 25 mol% or more, and more preferably 25 to 90 mol% relative to the total repeating units. Better, 25~85mol% is further better. By using a curable polysilsesquioxane compound (A) such that the ratio of the repeating unit represented by the formula (a-1) is 25 mol% or more relative to the total repeating units, a curable polysilsesquioxane compound with a lower refractive index can be obtained. sex composition.

The curable polysilsesquioxane compound (A) may further have a repeating unit (copolymer) represented by the following formula (a-2).

[chemical 4]

In the formula (a-2), R ² represents an unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

The unsubstituted C 1-10 alkyl group of ^R2 includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl , n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, etc.

Examples of the unsubstituted aryl group having 6 to 12 carbon atoms for R ² include phenyl, 1-naphthyl, 2-naphthyl and the like. As the substituent of the aryl group having a substituent carbon number of 6 to 12 as ^R2 , methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tri Alkyl groups such as butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and isooctyl; halogen atoms such as fluorine atom, chlorine atom, bromine atom, etc.; alkyl groups such as methoxy group and ethoxy group Oxygen.

Among these, as R ² , an unsubstituted alkyl group having 1 to 10 carbon atoms is preferred, and an unsubstituted alkyl group having 1 to 6 carbon atoms is preferable in order to easily obtain a cured product with higher adhesive strength and better heat resistance. An alkyl group is more preferred, and an unsubstituted alkyl group having 1 to 3 carbon atoms is particularly preferred.

When the curable polysilsesquioxane compound (A) has a repeating unit represented by formula (a-2), the curable polysilsesquioxane compound (A) may have one ^R2 , or Those having two or more kinds of R ² may be used.

When the curable polysilsesquioxane compound (A) has a repeating unit represented by formula (a-2), its ratio, relative to all repeating units, is preferably more than 0 mol%, and preferably less than 75 mol%. 10~75mol% is more preferable, and 15~75mol% is more preferable. By using the curable polysilsesquioxane compound (A) in which the ratio of the repeating unit represented by the formula (a-2) is within the above range, it becomes easy to obtain a polysilsesquioxane compound with higher adhesive strength and better heat resistance. Hardened.

The proportion of repeating units represented by formula (a-1) and formula (a-2) in the curable polysilsesquioxane compound (A), for example, can be determined by measuring the curable polysilsesquioxane compound (A) obtained from ²⁹ Si-NMR.

The curable polysilsesquioxane compound (A) is soluble in ketone-based solvents such as acetone; aromatic hydrocarbon-based solvents such as benzene; sulfur-containing solvents such as dimethylsulfene; and ether-based solvents such as tetrahydrofuran. ; ester-based solvents such as ethyl acetate; halogen-containing solvents such as chloroform; and various organic solvents such as mixed solvents composed of two or more of these. ²⁹ Si-NMR of the solution state of the siloxane compound (A).

The repeating unit represented by formula (a-1) and the repeating unit represented by formula (a-2) are those represented by the following formula (a-3).

[chemical 5]

[G represents (R ¹ -D) or R ² . R ¹ , D, and R ² represent the same meanings as above, respectively. O _1/2 means that the oxygen atom is shared with adjacent repeating units].

As shown in the formula (a-3), the curable polysilsesquioxane compound (A), generally referred to as the T position, has 3 oxygen atoms bonded to the silicon atom and 1 other group ( The group represented by G) is a partial structure composed of bonds. Examples of the T position contained in the curable polysilsesquioxane compound (A) include those represented by the following formulas (a-4) to (a-6).

[chemical 6]

In formulas (a-4), (a-5) and (a-6), G represents the same meaning as above. R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms for ^R include methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, and tertiary butyl. A plurality of R ³ may all be the same or different from each other. In addition, in the above-mentioned formulas (a-4) to (a-6), * is bonded to a silicon atom.

The T position represented by the formula (a-4) and the formula (a-5) contains a group (R ³ -O) that can provide polycondensation reaction. Therefore, polysilsesquioxane compounds containing more such T positions have better reactivity. In addition, compositions containing such polysilsesquioxane compounds have good curability. On the other hand, the T sites represented by the formulas (a-5) and (a-6) are bonded to two or more silicon atoms (silicon atoms at adjacent T sites). Therefore, a polysilsesquioxane compound containing many such T positions tends to have a larger molecular weight.

Therefore, a polysilsesquioxane compound containing many T positions represented by the formula (a-5) has a relatively large molecular weight and has sufficient reactivity. As explained below, the curable polysilsesquioxane compound (A) used in the present invention has these characteristics.

First, the curable polysilsesquioxane compound (A) satisfies the following condition 1. [Condition 1] When measuring ²⁹ Si-NMR of a curable polysilsesquioxane compound, peaks of 1 or 2 or more are observed in the region of -62ppm or more and less than -52ppm [region (2)]. 1 or 2 or more peaks are observed in at least one of the region of -52ppm to -45ppm [region (1)] and the region of -73ppm to -62ppm [region (3)], and, Z2 derived from the following formula is 20 to 40%. In addition, "the peak observed in the region (1)" refers to the range where the peak of the peak is in the region (1). The same applies to "peaks observed in the region (2)" and "peaks observed in the region (3)".

[number 3]

P1: Integral value in area (1) P2: Integral value in area (2) P3: Integral value in area (3).

In this specification, "integral value in the area (1)", "integral value in the area (2)", and "integral value in the area (3)" refer to -52ppm~-45ppm, -62ppm~-52ppm, -73ppm~-62ppm are calculated as the integral range.

The peaks observed in area (1), area (2), and area (3) come from the T positions shown in formula (a-4), formula (a-5), and formula (a-6) respectively silicon atom.

Therefore, the curable polysilsesquioxane compound that satisfies condition 1 contains 20 to 40% of the T site represented by the formula (a-5) with respect to the entire T site. This curable polysilsesquioxane compound has a large molecular weight as described above and has sufficient reactivity, which is advantageous as a curable component of a curable composition.

In condition 1, the value of Z2 is preferably 24~36%, more preferably 27~32%. When Z2 is too small, the reactivity is insufficient, and when Z2 is too large, the storage stability decreases.

For the curable polysilsesquioxane compound (A), when ²⁹ Si-NMR is measured, 1 or more peaks are observed in the region (3), and Z3 derived from the following formula takes 60 to 80% as good.

[number 4]

The curable polysilsesquioxane compound (A) in which Z3 is 60 to 80% contains 60 to 80% of the T site represented by the formula (a-6) relative to the entire T site. The value of Z3 is the curable polysilsesquioxane compound (A) in the range of 60-80%, which is a better balance of molecular weight and reactivity. In terms of the ease of obtaining this effect, the value of Z3 is better at 64-76%, and even better at 68-73%.

The values of Z2 and Z3 can be calculated according to the above-mentioned formula by measuring ²⁹ Si-NMR under the conditions described in the examples, for example, to obtain P1 to P3.

The curable polysilsesquioxane compound (A) satisfies the above-mentioned requirement 2. That is, the mass average molecular weight (Mw) of the curable polysilsesquioxane compound (A) is 4,000-11,000, preferably 4,000-8,000, more preferably 6,000-7,000.

As described above, the curable polysilsesquioxane compound satisfying condition 1 tends to have a relatively large molecular weight. Condition 2 is to clarify the range of the molecular weight. By using the curable polysilsesquioxane compound (A) having a mass average molecular weight (Mw) within the above range as a curable component, a curable composition that provides a cured product with high adhesive strength and excellent heat resistance can be obtained.

The molecular weight distribution (Mw/Mn) of the curable polysilsesquioxane compound (A) is not particularly limited, but is usually 1.0-10.0, preferably 1.1-6.0. By using a curable polysilsesquioxane compound (A) having a molecular weight distribution (Mw/Mn) within the above range as a curable component, a curable composition that provides a cured product with better adhesiveness and heat resistance can be obtained . The mass average molecular weight (Mw) and the number average molecular weight (Mn) are obtained as standard polystyrene conversion values, for example, according to gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

The curable polysilsesquioxane compound (A) can be obtained by, for example, compounding a compound represented by the following formula (a-7) (hereinafter sometimes referred to as "silane compound (1)"), or a silane Compound (1) and a compound represented by the following formula (a-8) (hereinafter, may be referred to as "silane compound (2)") are produced by polycondensation in the presence of a polycondensation catalyst.

[chemical 7]

In formulas (a-7) and (a-8), R ¹ , R ² , and D represent the same meanings as above. R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 10 carbon atoms, X ¹ and X ² each independently represent a halogen atom, and p and q each independently represent an integer of 0 to 3. A plurality of R ⁴ , R ⁵ , and a plurality of X ¹ , X ² may be the same as or different from each other.

Examples of the alkyl group having 1 to 10 carbon atoms for R ⁴ and R ⁵ include the same ones as the alkyl group having 1 to 10 carbon atoms for R ² . Examples of the halogen atoms for X ¹ and X ² include chlorine atoms, bromine atoms, and the like.

Examples of the silane compound (1) include CF ₃ Si(OCH ₃ ) ₃ , CF _{3 CF} 2 Si(OCH ₃ ) ₃ , CF 3 CF ₂ CF 2 Si(OCH ₃ ) ₃ , CF _{3 CF 2 CF 2 CF 2} Si(OCH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si( _{OCH 3} ) ₃ , CF ₃ CF ₂ CF ₂ CF 2 CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ CF 2 CF _{2 CF 2} CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , CF ₃ CF ₂ CF 2 CF ₂ CF ₂ CF ₂ CF ₂ CF _{2 CH 2 CH 2} Si(OCH ₃ ) ₃ , CF ₃ (C ₆ H ₄ )Si( OCH ₃ ) ₃ (4-(trifluoromethyl)phenyltrimethoxysilane), CF ₃ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si( _{OCH 2} CH ₃ ) ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH 2 CH ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ CF 2 CF ₂ CF ₂ CF _{2 CF 2} CF ₂ CF ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ , CF ₃ (C ₆ H ₄ )Si(OCH ₂ CH ₃ ) ₃ , 4-(trifluoromethyl)phenyltriethoxysilane, etc. Fluoroalkyltrialkoxysilane compounds; CF ₃ SiCl(OCH ₃ ) ₂ , CF ₃ CF ₂ SiCl(OCH ₃ ) ₂ , CF ₃ CF 2 CF ₂ SiCl(OCH 3 ) 2 , CF ₃ SiBr(OCH ₃ ) ₂ , CF ₃ SiBr(OCH 3 ) 2 ₃ ) ₂ , CF ₃ CF ₂ SiBr(OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ SiBr(OCH ₃ ) ₂ , CF ₃ CF 2 CF _{2 CF 2} SiCl(OCH ₃ ) ₂ , CF ₃ CH ₂ CH ₂ SiCl (OCH ₃ ) ₂ , CF ₃ CF ₂ CF 2 CF _{2 CH 2 CH 2} SiCl(OCH ₃ ) ₂ , CF ₃ CF 2 CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH _{2 SiCl} (OCH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF 2 CF _{2 CF 2 CF 2} CH ₂ CH ₂ SiCl(OCH ₃ ) ₂ , CF ₃ (C ₆ H ₄ )SiCl(OCH ₃ ) ₂ , 4-(trifluoromethyl)phenyl Chlorodimethoxysilane _, CF ₃ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF 2 CF ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CH ₂ CH ₂ SiCl(OCH ₂ CH ₃ ) ₂ , CF ₃ CF 2 CF ₂ CF ₂ CH ₂ CH _{2 SiCl} (OCH ₂ CH ₃ ) ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl(OCH ₂ CH ₃ ) ₂ 、CF ₃ CF ₂ CF ₂ CF ₂ CF 2 CF _{2 CF 2 CF 2} CH ₂ CH _{2 SiCl} (OCH ₂ CH ₃ ) ₂ , CF ₃ (C ₆ H ₄ )SiCl(OCH ₂ CH ₃ ) ₂ , 4-(trifluoromethyl)phenylchlorodiethoxysilane and other fluoroalkylhalogenated dialkoxysilane compounds; CF ₃ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF _{2 CF 2} SiCl ₂ (OCH ₃ ), CF ₃ CF 2 CF ₂ CF ₂ SiCl ₂ (OCH ₃ ), CF ₃ CH ₂ CH ₂ SiCl ₂ (OCH ₃ ), CF ₃ CF ₂ CF 2 CF ₂ CH _{2 CH 2 SiCl 2} (OCH ₃ ), CF ₃ CF 2 CF ₂ CF 2 CF _{2 CF 2 CH 2} CH _{2 SiCl 2} (OCH ₃ ), CF ₃ CF ₂ CF ₂ CF _{2 CF 2 CF 2} CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₂ (OCH ₃ ), CF ₃ (C ₆ H ₄ )SiCl ₂ (OCH ₃ ), 4-(trifluoro Methyl)phenyldichloromethoxysilane, _{CF 3} SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CF ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF 3 CF ₂ CF ₂ SiCl ₂ (OCH ₂ CH ₃ ) , CF ₃ CF ₂ CF ₂ CF ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CH ₂ CH ₂ SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ CF 2 CF ₂ CF ₂ CH ₂ CH _{2 SiCl 2} (OCH ₂ CH ₃ ), CF ₃ CF ₂ CF ₂ CF 2 CF ₂ CF ₂ CH _{2 CH 2 SiCl 2} (OCH ₂ CH ₃ ) ₂ , CF ₃ CF 2 CF ₂ CF 2 CF ₂ CF _{2 CF 2 CF 2} CH _{2 CH 2} Fluoroalkyl dihalides such as SiCl ₂ (OCH ₂ CH ₃ ), CF ₃ (C ₆ H ₄ )SiCl ₂ (OCH ₂ CH ₃ ), 4-(trifluoromethyl)phenyldichloroethoxysilane, etc. Oxysilane compounds; CF ₃ SiCl ₃ , CF ₃ CF ₂ SiCl ₃ , CF ₃ SiBr ₃ , CF ₃ CF ₂ SiBr ₃ , CF 3 CF ₂ CF ₂ SiCl ₃ , CF _{3 CF 2} CF ₂ CF ₂ SiCl ₃ , CF ₃ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF 2 _{CH 2} CH ₂ SiCl ₃ , CF ₃ CF 2 CF ₂ CF ₂ CF ₂ CF ₂ CH _{2 CH 2 SiCl 3} , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ (C ₆ H ₄ )SiCl ₃ , 4-trifluoromethylphenyltrichlorosilane, CF ₃ SiCl ₃ , CF ₃ CF ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ SiCl ₃ , CF ₃ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF 2 CF ₂ CF ₂ CH _{2 CH 2 SiCl 3} , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ SiCl ₃ , CF ₃ (C ₆ H ₄ )SiCl ₃ , 4- Fluoroalkyl trihalosilane compounds such as (trifluoromethyl)phenyltrichlorosilane. The silane compound (1) may be used alone or in combination of two or more. Among them, as the silane compound (1), those contained in fluoroalkyltrialkoxysilane compounds are preferable.

Examples of the silane compound (2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyl N-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, n-propyltributoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n- Alkyltrialkoxysilane compounds such as amyltrimethoxysilane, n-hexyltrimethoxysilane, and isooctyltriethoxysilane;

Methylchlorodimethoxysilane, Methylchlorodiethoxysilane, Methyldichloromethoxysilane, Methylbromodimethoxysilane, Ethylchlorodimethoxysilane, Ethylchlorodiethylsilane Oxysilane, ethyldichloromethoxysilane, ethylbromodimethoxysilane, n-propylchlorodimethoxysilane, n-propyldichloromethoxysilane, n-butylchlorodimethoxysilane Alkylhalogenated alkoxysilane compounds such as silane and n-butyldichloromethoxysilane; methyltrichlorosilane, methyltribromosilane, ethyltrichlorosilane, ethyltribromosilane, n-propyl Alkyl trihalogenation of trichlorosilane, n-propyltribromosilane, n-butyltrichlorosilane, isobutyltrichlorosilane, n-pentyltrichlorosilane, n-hexyltrichlorosilane, isooctyltrichlorosilane, etc. Silane compounds.

The silane compound (2) may be used alone or in combination of two or more.

Among them, as the silane compound (2), those contained in alkyltrialkoxysilane compounds are preferable.

The method for polycondensing the above-mentioned silane compound is not particularly limited, and a known method can be used. However, since the production of the curable polysilsesquioxane compound (A) has the following problems, it is necessary to examine the reaction conditions in particular.

One of the problems in the production of the curable polysilsesquioxane compound (A) is described in Patent Document 4 above. That is, referring to Table 1 of the above-mentioned Patent Document 4, it can be seen that the molecular weight of the obtained polymer tends to decrease due to the increase in the use ratio of the silane compound having a fluoroalkyl group.

As a result, the reactivity of the silane compound (1) and the reactivity of the silane compound (2) are greatly different, and it is difficult to obtain conditions that satisfy the conditions 1 and 2 if the previous knowledge about the polycondensation reaction of the silane compound (2) is used directly. 2 hardening polysilsesquioxane compounds.

In the examples of Patent Document 4, actually, a polycondensation reaction is carried out using a silane compound having a fluoroalkyl group to produce a polymer. However, as mentioned above, in the production method described in this document, since the mixing and cutting of the silane compound used in the reaction greatly affects the reaction, the molecular weight of the polymer cannot be controlled.

In addition, as described below, by using the reaction conditions described in the examples of Patent Document 4, although it is possible to Using silane compounds with poor reactivity (silane compounds with fluoroalkyl groups) as monomers, it is still difficult to obtain hardening polysilsesquioxane compounds satisfying conditions 1 and 2 even if this reaction condition is used (Comparative Examples 1 to 2). 3).

As a result of studying the polycondensation reaction using the silane compound (1), the inventors of the present invention found that by carrying out the polycondensation reaction under relatively mild conditions over a period of time, a hardening polymer that satisfies the conditions 1 and 2 can be obtained. semisiloxane compound.

Specifically, in a solvent, or without a solvent, use an appropriate amount of acid catalyst to carry out the polycondensation reaction of the silane compound at a predetermined temperature, and after obtaining a reaction solution containing an intermediate product, add an alkali to neutralize the reaction solution, and further carry out Polycondensation reaction, whereby hardening polysilsesquioxane compound (A) can be produced.

Examples of the solvent include water; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; acetone, methyl ethyl ketone, etc. Ketones such as methyl isobutyl ketone and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, and tertiary butanol. These solvents may be used alone or in combination of two or more.

When using a solvent, the amount used is usually 0.001-10.000 liter per mol of the total silane compound, preferably 0.010-0.9 liter.

Examples of the acid catalyst include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, and nitric acid; organic acids such as citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; . Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, citric acid, acetic acid and methanesulfonic acid is preferred.

The amount of the acid catalyst used is generally 0.01-2.00 mol%, preferably 0.05-1.00 mol%, more preferably 0.10-0.30 mol%, relative to the total mole amount of the silane compound.

The reaction temperature of the reaction in the presence of an acid catalyst is usually 20-90°C, preferably 25-80°C.

The reaction time of the reaction in the presence of an acid catalyst is usually 1 to 48 hours, preferably 3 to 24 hours.

The mass average molecular weight (Mw) of the intermediate product obtained by the reaction in the presence of an acid catalyst is usually 800-5,000, preferably 1,200-4,000.

As the base used when neutralizing the reaction solution, ammonia water; trimethylamine, triethylamine, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, aniline, Organic bases of picoline, 1,4-diazabicyclo[2.2.2]octane, imidazole, etc.; organic salt hydroxides of tetramethylamine hydroxide, tetraethylamine hydroxide, etc.; sodium methoxide , sodium ethoxide, sodium tertiary butoxide, potassium tertiary butoxide, etc. metal alkoxides; metal hydrides such as sodium hydride, potassium hydride, etc.; sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. Metal hydroxides; metal carbonates of sodium carbonate, potassium carbonate, magnesium carbonate, etc.; metal bicarbonates of sodium bicarbonate, potassium bicarbonate, etc.

The amount of alkali used in the neutralization of the reaction solution is usually 0.01~2.00mol%, preferably 0.05~1.00mol%, and more preferably 0.10~0.70mol%, relative to the total molar amount of the silane compound. .

In addition, the amount (mol) of the base used for the neutralization of the reaction solution is preferably 0.5 to 5.0 times the amount (mol) of the acid catalyst used before the first step, more preferably 0.8 to 3.0 times , 1.0~2.0 times is better.

The pH of the neutralized reaction solution is usually 6.0-8.0, preferably 6.2-7.0, more preferably 6.4-6.9.

The reaction temperature of the reaction after neutralization is usually 40-90°C, preferably 50-80°C.

The reaction time of the reaction after neutralization is usually 20 to 200 minutes, preferably 30 to 150 minutes.

In the above-mentioned production method, hydrolysis is the main purpose in the reaction in the presence of an acid catalyst, and dehydration condensation is the main purpose in the reaction after neutralization.

By carrying out the polycondensation reaction of the silane compound in this way, the curable polysilsesquioxane compound (A) can be efficiently produced.

After the reaction, the known purification treatment can be performed to separate the curable polysilsesquioxane compound (A).

In the curable composition of the present invention, the curable polysilsesquioxane compound (A) may be used alone or in combination of two or more.

The content of the curable polysilsesquioxane compound (A) in the curable composition of the present invention is usually 40 to 80% by mass, or 50 to 70% by mass based on the entire solid content of the curable composition. better.

[(E) component] Component (E) constituting the curable composition of the present invention is fine particles having an average primary particle diameter of more than 0.04 μm and not more than 8 μm (hereinafter sometimes referred to as “fine particles (E)”).

By using a curable composition containing fine particles (E), a cured product having excellent peeling resistance can be formed. From the viewpoint of easily obtaining this effect, the average primary particle size of the microparticles (E) is preferably 0.06-7 μm, more preferably 0.3-6 μm, and still more preferably 0.5-4 μm.

The average primary particle diameter of the microparticles (E) is determined by the laser scattering method using a laser diffraction-scattering particle size distribution measuring device (for example, manufactured by Horiba Seisakusho Co., Ltd., product name "LA-920") or the like. obtained from the measurement.

The shape of the microparticles (E) may be spherical, chain-like, needle-like, plate-like, flake-like, rod-like, or fibrous, but spherical shape is preferred. Here, the spherical shape refers to a substantially spherical shape including a polyhedral shape that can approximate a sphere, such as an ellipsoid, an egg shape, a gold flat sugar shape, and a pupal shape, in addition to a spherical shape.

The constituents of the microparticles (E) are not particularly limited, and include metals; metal oxides; minerals; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; Metal hydroxides such as aluminum silicate, calcium silicate, magnesium silicate, etc.; inorganic components such as silicon dioxide; polysiloxane; organic components such as acrylic polymers, etc. In addition, the microparticles (E) used may be surface-modified.

Metal refers to in the periodic table, belonging to group 1 (except H), group 2~11, group 12 (except Hg), group 13 (except B), group 14 (except C and Si), group 15 (N, P, As and Sb excluded) or Group 16 elements (O, S, Se, Te and Po excluded).

Examples of metal oxides include titanium oxide, aluminum oxide, diaspore, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, zinc oxide, and composite oxides thereof. The fine particles of metal oxides also include sol particles composed of the metal oxides.

Examples of minerals include smectite, bentonite, and the like. Examples of smectite include montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, Sauconite, etc. Examples of silica include dry silica, wet silica, surface-modified silica (surface-modified silica), and the like.

Fine particles (E) may be used alone or in combination of two or more. Among them, from the viewpoint of easiness to obtain the above-mentioned effect, as the fine particles (E), at least one kind of fine particles selected from the group consisting of metal oxide, silicon dioxide, and polysiloxane whose surface is covered with polysiloxane is preferable. , silicon dioxide and polysiloxane are more preferable.

The content of the microparticles (E) [(E) component] in the curable composition of the present invention is not particularly limited, but the amount is based on the mass ratio of (A) component to (E) component [(A) component: (E) ) composition], preferably 100:0.1~100:40, more preferably 100:0.2~100:30, more preferably 100:0.3~100:20, and 100:0.5~100:15 More preferably, 100:0.8~100:12 is further more preferable. By using (E)component in the said range, the effect of adding (E)component can be expressed more.

The curable composition of the present invention may contain a silane coupling agent (hereinafter, sometimes referred to as "silane coupling agent (B)") having a nitrogen atom in the molecule as the component (B).

The curable composition containing the silane coupling agent (B) provides a cured product with better workability in the coating step, and better adhesiveness, peel resistance and heat resistance. Here, the term "good operability in the coating step" means that in the coating step, the curable composition is output from the delivery tube, and when the delivery tube is pulled up, there is little amount of threading, or it is broken immediately. By using a curable composition having this property, it is possible to prevent contamination of the surrounding area due to splashing of the resin and diffusion of liquid droplets.

The silane coupling agent (B) is not particularly limited as long as it has a nitrogen atom in the molecule. For example, a trialkoxysilane compound represented by following formula (b-1), a dialkoxyalkylsilane compound or a dialkoxyarylsilane compound represented by formula (b-2), etc. are mentioned.

[chemical 8]

In the above formula, R ^a represents an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tertiary butoxy. A plurality of R ^a may be the same as or different from each other. R ^b represents an alkyl group with 1 to 6 carbons such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, etc.; or phenyl, 4-chlorophenyl, 4-toluene A substituted or unsubstituted aryl group such as a group, 1-naphthyl group or the like.

R ^c represents an organic group having 1 to 10 carbon atoms having a nitrogen atom. In addition, R ^c may further bond with other groups containing silicon atoms. Specific examples of organic groups having 1 to 10 carbon atoms in R ^c include N-2-(aminoethyl)-3-aminopropyl, 3-aminopropyl, N-(1,3 -Dimethyl-butylene)aminopropyl, 3-ureidopropyl, N-phenyl-aminopropyl and the like.

Among the compounds represented by the above-mentioned formula (b-1) or (b-2), when R ^c is an organic group bonded to other silicon atom-containing groups, the compound obtained by isocyanurate (isocyanurate) can be mentioned. Isocyanuric acid-based silane coupling agents composed of skeletons bonded to other silicon atoms, and urea-based silane coupling agents composed of urea skeletons bonded to other silicon atoms.

Among them, as the silane coupling agent (B), it is preferable to use an isocyanuric acid-based silane coupling agent and a urea-based silane coupling agent in terms of easily obtaining a hardened product with higher adhesive strength. Those having 4 or more alkoxy groups bonded to silicon atoms are preferred. An alkoxy group having 4 or more silicon atoms bonded means that the total number of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is 4 or more.

As the isocyanuric acid-based silane coupling agent having 4 or more alkoxy groups bonded to silicon atoms, compounds represented by the following formula (b-3) can be cited. Examples of the alkoxy urea-based silane coupling agent include compounds represented by the following formula (b-4).

[chemical 9]

In the formula, R ^a represents the same meaning as above. t1 to t5 each independently represent an integer of 1 to 10, preferably an integer of 1 to 6, particularly preferably 3.

Specific examples of the compound represented by the formula (b-3) include 1,3,5-N-para(3-trimethoxysilylpropyl)isocyanuric acid, 1,3,5,- N-ginseng (3-triethoxysilylpropyl) isocyanuric acid, 1,3,5,-N-ginseng (3-triisopropoxysilylpropyl) isocyanuric acid, 1,3,5,-N-paraffin (3-tributoxysilylpropyl) isocyanuric acid and other 1,3,5-N-paraffin [(three (carbon number 1~6) alkoxy base) silicon base (carbon number 1~10) alkyl] trimeric isocyanic acid; 1,3,5,-N-paraffin(3-dimethoxymethylsilylpropyl)isocyanuric acid, 1,3,5,-N-paraffin(3-dimethoxyethylsilyl propyl) isocyanuric acid, 1,3,5,-N-paraffin (3-dimethoxyisopropylsilylpropyl)isocyanuric acid, 1,3,5,-N- ginseng(3-dimethoxyn-propylsilylpropyl)isocyanuric acid, 1,3,5,-N-paraffin(3-dimethoxyphenylsilylpropyl)isocyanuric acid Acid, 1,3,5,-N-paraffin (3-diethoxymethylsilylpropyl)isocyanuric acid, 1,3,5,-N-paraffin (3-diethoxyethyl Silylpropyl) isocyanuric acid, 1,3,5,-N-paraffin (3-diethoxyisopropylsilylpropyl)isocyanuric acid, 1,3,5,- N-paraffin (3-diethoxyn-propylsilylpropyl) isocyanuric acid, 1,3,5,-N-paraffin (3-diethoxyphenylsilylpropyl) trimer Isocyanic acid, 1,3,5,-N-paraffin (3-diisopropoxymethylsilylpropyl) isocyanuric acid, 1,3,5,-N-paraffin (3-diiso Propoxyethylsilylpropyl) isocyanuric acid, 1,3,5,-N-ginseng (3-diisopropoxyisopropylsilylpropyl)isocyanuric acid, 1, 3,5,-N-paraffin (3-diisopropoxy-n-propylsilylpropyl)isocyanuric acid, 1,3,5,-N-paraffin (3-diisopropoxyphenyl Silylpropyl) isocyanuric acid, 1,3,5,-N-paraffin (3-dibutoxymethylsilylpropyl)isocyanuric acid, 1,3,5,-N- ginseng(3-dibutoxyethylsilylpropyl)isocyanuric acid, 1,3,5,-N-ginseng(3-dibutoxyisopropylsilylpropyl)isocyanuric acid Acid, 1,3,5,-N-paraffin (3-dibutoxy-n-propylsilylpropyl)isocyanuric acid, 1,3,5,-N-paraffin (3-dibutoxy 1,3,5-N-para[(di(carbon number 1~6)alkoxy)silyl(carbon number 1~10)alkyl]tri Polyisocyanic acid, etc.

Specific examples of the compound represented by the formula (b-4) include N,N'-bis(3-trimethoxysilylpropyl)urea, N,N'-bis(3-triethoxysilyl) propyl)urea, N,N'-bis(3-tripropoxysilylpropyl)urea, N,N'-bis(3-tributoxysilylpropyl)urea, N,N' - N,N'-bis[(tri(1-6 carbon number)alkoxysilyl)(carbon number 1-10)alkyl]urea such as bis(2-trimethoxysilylethyl)urea; N,N'-bis(3-dimethoxymethylsilylpropyl)urea, N,N'-bis(3-dimethoxyethylsilylpropyl)urea, N,N'-bis (3-diethoxymethylsilylpropyl)urea and other N,N'-bis[(di(carbon number 1~6)alkoxy(carbon number 1~6)alkylsilyl(carbon number 1~10) Alkyl]urea; N,N'-bis(3-dimethoxyphenylsilylpropyl)urea, N,N'-bis(3-diethoxyphenylsilylpropyl) )N,N'-bis[(di(carbon number 1~6)alkoxy(carbon number 6~20)arylsilyl(carbon number 1~10)alkyl]urea, etc.

A silane coupling agent (B) can be used individually by 1 type, or in combination of 2 or more types.

Among them, as the silane coupling agent (B), 1,3,5-N-paraffin (3-trimethoxysilylpropyl) isocyanuric acid, 1,3,5-N-paraffin ( 3-triethoxysilylpropyl)isocyanuric acid (hereinafter referred to as "isocyanuric acid compound"), N,N'-bis(3-trimethoxysilylpropyl)urea, A combination of N,N'-bis(3-triethoxysilylpropyl)urea (hereinafter referred to as "urea compound") and the above-mentioned isocyanuric acid compound and urea compound is preferable.

When using the combination of the above-mentioned isocyanuric acid compound and urea compound, the ratio of the two is preferably 100:1 to 100:200 in mass ratio of (isocyanuric acid compound) to (urea compound), and 100: 10~100: 110 is better. By using a combination of an isocyanuric acid compound and a urea compound at such a ratio, it is possible to obtain a curable composition that provides a cured product with higher adhesive strength and better heat resistance.

When the curable composition of the present invention contains a silane coupling agent (B) [(B) component], the content of (B) component is not particularly limited, but the amount is based on the mass ratio of the above-mentioned (A) component to (B) component [(A) component: (B) component], preferably 100:0.1~100:90, more preferably 100:0.3~100:60, more preferably 100:1~100:50, preferably 100 :3~100:40 is further better, and the amount of 100:5~100:30 is particularly preferable. The cured product of the curable composition containing (A) component and (B) component in such a ratio has higher adhesive strength and better heat resistance.

The curable composition of the present invention may contain a silane coupling agent (hereinafter, sometimes referred to as "silane coupling agent (C)") having an acid anhydride structure in the molecule as the component (C). The curable composition containing the silane coupling agent (C) provides a cured product with good handling properties in the coating step, higher adhesive strength, and better peel resistance and heat resistance.

Examples of the silane coupling agent (C) include 2-(trimethoxysilyl)ethylsuccinic anhydride, 2-(triethoxysilyl)ethylsuccinic anhydride, 3-(trimethoxysilyl)propyl tri(carbon number 1~6) alkoxysilyl (carbon number 2~8) alkyl succinic anhydrides such as triethoxysilyl succinic anhydride, 3-(triethoxysilyl)propyl succinic anhydride, etc.; 2-(dimethoxymethylsilyl) ethyl succinic anhydride and other di(carbon number 1~6) alkoxymethylsilyl (carbon number 2~8) alkyl succinic anhydrides; 2-(Methoxydimethylsilyl) ethyl succinic anhydride and other (carbon number 1~6) alkoxydimethylsilyl (carbon number 2~8) alkyl succinic anhydrides;

2-(trichlorosilyl)ethylsuccinic anhydride, 2-(tribromosilyl)ethylsuccinic anhydride, silicon trihalide (carbon number 2~8) alkyl succinic anhydride, etc.; 2-(Dichloromethylsilyl) ethyl succinic anhydride and other dihalogenated methylsilyl (carbon number 2~8) alkyl succinic anhydrides; 2-(Chlorodimethylsilyl) ethyl succinic anhydride, etc. Halogenated dimethylsilyl (2-8 carbon atoms) alkyl succinic anhydride, etc. A silane coupling agent (C) can be used individually by 1 type, or in combination of 2 or more types.

Among them, as the silane coupling agent (C), tri(carbon number 1~6) alkoxysilyl (carbon number 2~8) alkyl succinic anhydride is preferred, and 3-(trimethoxysilyl) Propylsuccinic anhydride or 3-(triethoxysilyl)propylsuccinic anhydride is particularly preferred.

When the curable composition of the present invention contains a silane coupling agent (C) [(C) component], the content of the (C) component is not particularly limited, but the amount is based on the mass ratio of the above-mentioned (A) component to (C) component [ (A) Component: (C) Component], preferably 100:0.1~100:30, more preferably 100:0.3~100:20, more preferably 100:0.5~100:15, preferably 100:0.5~100:15 100:1~100:10 is more preferable. The cured product of the curable composition containing the component (C) in such a ratio has higher adhesive strength.

The curable composition of the present invention may contain fine particles having an average primary particle diameter of 5 to 40 nm (hereinafter, sometimes referred to as "fine particles (D)") as the component (D). A curable composition containing fine particles (D) has good handleability in the coating step. From the viewpoint of easily obtaining this effect, the average primary particle size of the microparticles (D) is preferably 5-30 nm, more preferably 5-20 nm.

The average primary particle diameter of the microparticles (D) can be obtained by observing the shape of the microparticles using a transmission electron microscope.

The specific surface area of the microparticles (D) is preferably 10 to 500 m ² /g, more preferably 20 to 300 m ² /g. When the specific surface area is within the above range, it becomes easy to obtain a curable composition with good handleability in the coating step. The specific surface area can be obtained by the BET multi-point method.

The shape of the microparticles (D) may be spherical, chain-like, needle-like, plate-like, flake-like, rod-like, or fibrous, but spherical shape is preferred. Here, the spherical shape refers to a substantially spherical shape including a polyhedron shape that can approximate a sphere, such as an ellipsoid, an egg shape, a flat candy shape, and a cocoon shape, in addition to a spherical shape.

Examples of the constituents of the microparticles (D) include the same ones as those exemplified as the constituents of the microparticles (E). Fine particles (D) may be used alone or in combination of two or more. Among these, silicon dioxide, metal oxides, and minerals are preferable as fine particles (D), and silicon dioxide is more preferable in terms of obtaining a hardened product with good transparency.

Among the silicas, the surface-modified silica is preferable, and the water-repellent surface-modified silica is more preferable in view of the ease of obtaining a curable composition with better workability in the coating step. Examples of water-repellent surface-modified silica include, on the surface, a trialkylsilyl group with 1 to 20 carbon atoms such as trimethylsilyl, and a trialkylsilyl group with 1 to 20 carbon atoms such as dimethylsilyl. Alkylsilyl; octylsilyl and other alkyl-bonded silica with 1 to 20 carbon atoms; silica treated with polysiloxane oil on the surface, etc. Hydrophobic surface-modified silica can be obtained by, for example, using a trialkylsilyl group with a three-carbon number of 1-20, an alkylsilyl group with a two-carbon number of 1-20, and a carbon number of Surface modification with silane coupling agent such as alkyl silyl group of 1~20, or silicon dioxide particles treated with polysiloxane oil. In addition, as the surface-modified silica, a commercially available product can be used as it is.

When the curable composition of the present invention contains microparticles (D) [(D) component], the content of (D) component is not particularly limited, but the amount is based on the mass ratio of the above-mentioned (A) component to (D) component [( A) Components: (D) Components], preferably 100:0.1~100:90, more preferably 100:0.2~100:60, more preferably 100:0.3~100:50, 100 : 0.5~100:40 is better, 100:0.8~100:30 is better. By using (D)component in the said range, the effect of adding (D)component can be expressed more.

The curable composition of the present invention may contain other components (component (F)) other than the above-mentioned components (A) to (E) within the range that does not hinder the object of the present invention. As (F) component, antioxidant, a ultraviolet absorber, a light stabilizer, etc. are mentioned.

Antioxidants are added to prevent oxidative deterioration during heating. Examples of antioxidants include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and the like.

Examples of phosphorus-based antioxidants include phosphites, oxaphosphaphenanthrene oxides, and the like. Examples of the phenolic antioxidant include monophenols, bisphenols, high molecular weight phenols, and the like. Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearoyl-3, 3'-thiodipropionate, etc.

These antioxidants may be used alone or in combination of two or more. The usage-amount of an antioxidant is 10 mass % or less normally with respect to (A) component.

The ultraviolet absorber is added for the purpose of improving the light resistance of the obtained cured product. Examples of the ultraviolet absorber include salicylic acids, benzophenones, benzotriazoles, hindered amines, and the like. The ultraviolet absorber may be used alone or in combination of two or more. The usage-amount of a ultraviolet absorber is 10 mass % or less normally with respect to (A) component.

The light stabilizer is added for the purpose of improving the light resistance of the obtained cured product. As the light stabilizer, for example, poly[{6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidine)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidine)imino} ] and other hindered amines. These photostabilizers may be used alone or in combination of two or more. (F) The total usage-amount of a component is 20 mass % or less normally with respect to (A) component.

The curable composition of the present invention may also contain a solvent. The solvent is not particularly limited as long as it can dissolve or disperse the components of the curable composition of the present invention. As the solvent, a solvent having a boiling point of 254° C. or higher (hereinafter, may be described as “a solvent (S1)”) is preferable. The boiling point of the solvent (S1) is above 254°C, preferably 254~300°C. Here, the boiling point means the boiling point at 1013 hPa (it is the same in this specification).

The solvent (S1) is not particularly limited as long as it has a boiling point of 254° C. or higher and can dissolve the curable polysilsesquioxane compound (A). This type of solvent (S1) has a relatively slow volatilization speed. Therefore, since the curable composition containing the solvent (S1) has little change in viscosity even after being left for a long time after coating, it is possible to mount an optical element or the like excellently like immediately after coating.

As the solvent (S1), specifically, triethylene glycol n-butyl ether (boiling point 274°C), 1,6-hexanediol diacrylate (boiling point 260°C), diethylene glycol dibutyl ether (boiling point 256°C), triethylene glycol butyl methyl ether (boiling point 261°C), polyethylene glycol dimethyl ether (boiling point 264~294°C), tetraethylene glycol dimethyl ether (boiling point 275°C), polyethylene glycol monomethyl ether Ether (boiling point 290~310°C), etc. Among them, as the solvent (S1), tripropylene glycol n-butyl ether and 1,6-hexanediol diacrylate are preferable from the viewpoint of obtaining the effect of the present invention more easily. The solvent (S1) may be used alone or in combination of two or more.

The curable composition of the present invention may contain solvents other than the solvent (S1). The solvent other than the solvent (S1) is preferably a solvent having a boiling point of not less than 200°C and not more than 254°C (hereinafter, sometimes referred to as "the solvent (S2)"). The solvent (S2) is not particularly limited as long as it has a boiling point of 200° C. to less than 254° C. and can dissolve the curable polysilsesquioxane compound (A). The curability of the curable composition is improved by using the solvent (S1) and the solvent (S2) in combination.

Specific examples of the solvent (S2) include diethylene glycol monobutyl ether acetate (boiling point 247°C), dipropylene glycol n-butyl ether (boiling point 229°C), benzyl alcohol (boiling point 204.9°C), dipropylene glycol Methyl ether acetate (boiling point 209°C), diethylene glycol butyl methyl ether (boiling point 212°C), dipropylene glycol n-propyl ether (boiling point 212°C), tripropylene glycol dimethyl ether (boiling point 215°C), triethylene glycol Alcohol dimethyl ether (boiling point 216°C), diethylene glycol monoethyl ether acetate (boiling point 217.4°C), diethylene glycol n-butyl ether (boiling point 230°C), ethylene glycol monophenyl ether (boiling point 245°C), Tripropylene glycol methyl ether (boiling point 242°C), propylene glycol phenyl ether (boiling point 243°C), triethylene glycol monomethyl ether (boiling point 249°C), etc. Among these, as the solvent (S2), in terms of the ease of obtaining its effect, alcohol-based solvents are preferred, diethylene glycol monobutyl ether acetate and dipropylene glycol n-butyl ether are preferred, and diethylene glycol monobutyl ether acetate is preferred. Alcohol monobutyl ether acetate is more preferred.

When the solvent (S1) and the solvent (S2) are used together, specifically, a combination of tripropylene glycol n-butyl ether (the solvent (S1)) and diethylene glycol monobutyl ether acetate (the solvent (S2)), A combination of 1,6-hexanediol diacrylate (vehicle (S1)) and diethylene glycol monobutyl ether acetate (vehicle (S2)), tripropylene glycol n-butyl ether (vehicle (S1)) and A combination of dipropylene glycol n-butyl ether (vehicle (S2)) and a combination of 1,6-hexanediol diacrylate (vehicle (S1)) and dipropylene glycol n-butyl ether (organic solvent (S2)) are preferable.

When the curable composition of the present invention contains a solvent, its content is such that the solid content concentration becomes preferably 50 to 95% by mass, more preferably 60 to 85% by mass. By setting the solid content concentration within this range, it becomes easy to obtain a curable composition with good handleability in the coating step.

When the curable composition of the present invention contains the solvent (S1) and/or the solvent (S2), the total amount of these solvents is usually 50 to 100% by mass, preferably 70 to 100% by mass, based on the total solvent. 90~100% by mass is more preferable.

When the curable composition of the present invention contains a solvent (S1), the content of the solvent (S1) is usually 20 to 100% by mass, preferably 30 to 85% by mass, based on the total amount of the solvent (S1) and the solvent (S2). Preferably, 50-80% by mass is more preferable.

A curable composition that satisfies these conditions related to the amount of the solvent has an appropriate balance between adhesiveness and wet spreadability (the above-mentioned characteristics related to droplet spreading).

The curable composition of this invention can be prepared, for example, by mixing said (A) component, (E) component, and components other than these in a specific ratio as needed, and degassing. The mixing method and the degassing method are not particularly limited, and known methods can be used.

The curable composition of the present invention contains a curable polysilsesquioxane compound (A). Therefore, the curable composition of the present invention has good curability and low refractive index. In addition, the curable composition of the present invention is advantageous as a material for forming a cured product having high adhesive strength.

The refractive index (nD) at 25° C. of the curable composition of the present invention is usually 1.380 to 1.434, preferably 1.380 to 1.430, more preferably 1.380 to 1.428, and still more preferably 1.380 to 1.425. The refractive index (nD) of a curable composition can be measured by the method described in an Example.

In addition, the curable composition of this invention contains (E)component. Therefore, as described below, by using the curable composition of the present invention, a cured product having excellent peeling resistance can be formed.

2) Hardened The cured product of the present invention is obtained by curing the curable composition of the present invention. As a method of hardening the curable composition of this invention, heating hardening is mentioned. The heating temperature for hardening is usually 100-200°C, and the heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

The cured product of the present invention has high bonding strength and good heat resistance. Whether or not the cured product of the present invention has these characteristics can be confirmed as follows, for example. That is, a specific amount of the curable composition of the present invention is coated on the mirror surface of a silicon wafer, the coated surface is mounted on an adherend, pressed, and heat-treated to be cured. Place it on the measuring table of the bond strength testing machine preheated to a predetermined temperature (for example, 23°C, 100°C) for 30 seconds, near the position of 50 μm height from the adherend, in the horizontal direction relative to the bonding surface (shear Tangential direction) to apply stress to measure the adhesive force between the test piece and the adherend.

The adhesive force of the cured product of the present invention is preferably at least 60N/ ^4mm2 at 23°C, more preferably at least 80N/ ^4mm2 , and particularly preferably at least 100N/ ^4mm2 . In addition, the adhesion force of the cured product is preferably 30N/4mm2 ^or above at 100°C, more preferably 40N/4mm2 ^or above, still more preferably 50N/4mm2 ^or above, and especially 60N/ ^4mm2 or above good. In this specification, "4mm ² " means 2mm x 2mm (a square with a side of 2mm).

In addition, the cured product of the present invention is obtained by curing the curable composition containing the component (E), and is excellent in peeling resistance. Whether or not the cured product of the present invention has good peeling resistance can be confirmed, for example, as follows. On the LED lead frame, apply the curable composition, press the sapphire wafer, heat it at 170°C for 2 hours to harden it, pour the sealing material into the cup, heat it at 120°C for 1 hour, and then add it at 150°C It heat-processed at ℃, and obtained the test piece of hardened|cured material. The test piece was exposed to an environment of 85°C and 85%RH for 168 hours, and was treated with IR reflow with a heating time of 1 minute at a temperature of 160°C and a maximum temperature of 260°C. The test of standing for 30 minutes each at °C and +100°C was regarded as one cycle, and 500 cycles were implemented. Thereafter, the sealing material was removed, and it was checked whether or not the elements were peeled off together at this time. In the cured product of the present invention, the probability of peeling is usually 50% or less, more preferably 25% or less.

Due to the above properties, the cured product of the present invention is suitable for use as an optical element fixing material.

3) How to use the curable composition The method of the present invention is a method of using the curable composition of the present invention as an adhesive for an optical element fixing material or a sealing material for an optical element fixing material. Examples of the optical element include light-emitting elements such as LEDs and LDs, light-receiving elements, composite optical elements, and optical integrated circuits.

(Adhesive for optical element fixing material) The curable composition of the present invention is suitably used as an adhesive for optical element fixing materials. As a method of using the curable composition of the present invention as an adhesive for an optical element fixing material, coating the adhesive surface on one or both sides of a material to be bonded (optical element and its substrate, etc.) After the composition is pressed, it is heated and hardened, and the materials to be bonded are firmly bonded to each other. The application amount of the curable composition of the present invention is not particularly limited, as long as it is an amount capable of firmly bonding materials to be bonded by curing the composition. Usually, the thickness of the coating film of a curable composition is 0.5-5 micrometers, Preferably it is 1-3 micrometers.

Substrate materials for bonding optical elements include glass such as soda-lime glass and heat-resistant hard glass; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium and their metal alloys, Metals such as stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, Polystyrene, polycarbonate, polymethylpentene, polyether ether ketone, polyether ether ketone, polyphenylene sulfide, polyether imide, polyimide, polyamide, acrylic resin, Synthetic resins such as norbornene-based resins, cycloolefin resins, glass epoxy resins, etc.

The heating temperature for heating and hardening depends on the curable composition used and the like, but is usually 100 to 200°C. The heating time is usually from 10 minutes to 20 hours, preferably from 30 minutes to 10 hours.

>Sealing material for optical element fixing material> The curable composition of the present invention is suitably used as a sealing material for optical element fixing materials. As a method of using the curable composition of the present invention as a sealing material for an optical element fixing material, for example, after molding the composition into a desired shape to obtain a molded body containing an optical element, by using It is hardened by heating, a method of manufacturing an optical element sealing body, and the like. The method for molding the curable composition of the present invention into a desired shape is not particularly limited, and known molding methods such as transfer molding and injection molding can be used.

The heating temperature during heat curing depends on the curable composition used, etc., but is usually 100 to 200°C. The heating time is usually from 10 minutes to 20 hours, preferably from 30 minutes to 10 hours.

Since the obtained optical element sealing body uses the curable composition of this invention, it is excellent in heat resistance, and adhesive strength is high. [Example]

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to those of the following examples. Parts and % in each example are mass standards unless otherwise specified.

(Example 1) After introducing 17.0 g (77.7 mmol) of 3,3,3-trifluoropropyltrimethoxysilane and 32.33 g (181.3 mmol) of methyltriethoxysilane into a 300 mL eggplant-shaped flask, While stirring this, an aqueous solution obtained by dissolving 0.0675 g of 35% hydrochloric acid (0.65 mmol of HCl, 0.25 mol % relative to the total amount of silane compounds) in 14.0 g of distilled water was added, and the whole was stirred at 30° C. for 2 hours, then heated to 70°C and stirred for 20 hours. While continuing to stir the contents, a mixed solution of 28% ammonia water 0.0394g (the amount of _NH3 is 0.65mmol) and propyl acetate 46.1g was added thereto to make the pH of the reaction solution 6.9, and it was directly stirred at 70°C for 60 minutes. After the reaction liquid was left to cool to room temperature, 50 g of propyl acetate and 100 g of water were added thereto for liquid separation treatment to obtain an organic layer containing a reaction product. Magnesium sulfate was added to this organic layer for drying treatment. After removing magnesium sulfate by filtration, the organic layer was concentrated with a distiller, and then, the obtained concentrate was vacuum-dried to obtain a curable polysilsesquioxane compound (1).

To 100 parts of curable polysilsesquioxane compound (1), add 20 parts of silica filler with an average primary particle diameter of 7 nm, and 10 parts of polysiloxane filler with an average primary particle diameter of 0.8 μm. Furthermore, after adding 30 parts of diethylene glycol monobutyl ether acetate as a solvent: Tripropylene glycol n-butyl ether=40:60 (mass ratio) mixed solvent, the whole thing was stirred. After dispersion treatment by triple roll mill, 30 parts of 1,3,5-N-para[3-(trimethoxysilyl)propyl]isocyanuric acid, 3-( 3 parts of trimethoxysilyl) propyl succinic anhydride, moreover, the mixed solvent of diethylene glycol monobutyl ether acetate as solvent: tripropylene glycol n-butyl ether=40:60 (mass ratio), fully The whole was mixed and degassed to obtain a curable composition (1) with a solid content concentration of 82%.

(Example 2) Except that the stirring time after adding the mixed solution of 28% ammonia water and propyl acetate was changed to 120 minutes, all the other were the same as in Example 1 to obtain the hardening polysilsesquioxane compound (2) and the hardening composition ( 2).

(Example 3) Except that the stirring time after adding the mixed solution of 28% ammonia water and propyl acetate was changed to 90 minutes, all the other were the same as in Example 1 to obtain the hardening polysilsesquioxane compound (3) and the hardening composition ( 3).

(Example 4) Except that the stirring time after adding the mixed solution of 28% ammonia water and propyl acetate was changed to 50 minutes, all the other were the same as in Example 1 to obtain the hardening polysilsesquioxane compound (4) and the hardening composition ( 4).

(Example 5) Except that the stirring time after adding the mixed solution of 28% ammonia water and propyl acetate was changed to 40 minutes, all the other were the same as in Example 1 to obtain hardening polysilsesquioxane compound (5) and hardening composition ( 5).

(Comparative Example 1) According to the method of Example 8 of WO2017/110948, a curable polysilsesquioxane compound (6) was obtained. Next, 20 parts of silica filler with an average primary particle diameter of 7 nm and 10 parts of polysiloxane filler with an average primary particle diameter of 0.8 μm were added to 100 parts of curable polysilsesquioxane compound (6). Furthermore, after adding 30 parts of diethylene glycol monobutyl ether acetate as a solvent, the whole was stirred. After dispersing with a three-axis rolling mill, add 10 parts of 1,3,5-N-para[3-(trimethoxysilyl)propyl]isocyanuric acid, 3-(trimethoxysilyl) 3 parts of propyl succinic anhydride, and diethylene glycol monobutyl ether acetate was added so that the viscosity when measured with an E-type viscometer at 25°C and 200 s ^-1 became 4.5 Pa·s , fully mixed the whole, and degassed to obtain a curable composition (6). In addition, in paragraph (0115) of WO2017/110948, although the amount of hydrochloric acid used is described as "0.25 mol% relative to the total amount of silane compounds", when calculating from the amount introduced, it is correctly "0.25 mol% relative to the amount of silane compounds". The total amount is about 1.6 mol%. The same applies to Comparative Examples 2 and 3 below.

(comparative example 2) According to the method of Example 9 of WO2017/110948, a curable polysilsesquioxane compound (7) was obtained. Next, according to the method similar to Comparative Example 1, curable composition (7) was obtained.

(comparative example 3) According to the method of Example 10 of WO2017/110948, a curable polysilsesquioxane compound (8) was obtained. Next, according to the same method as Comparative Example 1, a curable composition (8) was obtained.

(Comparative Example 4) In a 300mL eggplant-shaped flask, 71.37g (400mmol) of methyltriethoxysilane was introduced, and while stirring, 0.1g of 35% hydrochloric acid dissolved in 21.6g of distilled water (relative to the amount of silane compound) was added. The total amount was 0.25 mol %) of the aqueous solution, the whole was stirred at 30° C. for 2 hours, and then the temperature was raised to 70° C. and stirred for 5 hours. While continuing to stir the contents, 140 g of propyl acetate and 0.12 g of 28% ammonia water (0.5 mol% of NH ₃ relative to the total amount of silane compounds) were added thereto, and stirred at 70° C. for 3 hours. After cooling the reaction liquid to room temperature, the organic layer was washed with pure water until the pH of the aqueous layer became 7. The organic layer was concentrated with a distiller, and the concentrate was vacuum-dried to obtain a curable polysilsesquioxane compound (9). Next, by the same method as in Example 1, a curable composition (9) was obtained.

(comparative example 5) Except that the stirring time after adding the mixed solution of 28% ammonia water and propyl acetate was changed to 240 minutes, all the other were the same as in Example 1 to obtain the hardening polysilsesquioxane compound (10) and the hardening composition ( 10).

Using curable polysilsesquioxane compounds (1) to (10) and curable compositions (1) to (10) obtained in Examples and Comparative Examples, the following measurements and tests were performed, respectively. The results are shown in Table 1.

[Measurement of mass average molecular weight] The mass average molecular weight (Mw) of a curable polysilsesquioxane compound was measured with the following apparatus and conditions. Device name: HLC-8220GPC, manufactured by Tosoh Co., Ltd. Column: connected to TSKgel GMHXL, TSKgel GMHXL and TSKgel 2000HXL in sequence Solvent: Tetrahydrofuran Standard material: polystyrene Injection volume: 20μl Measuring temperature: 40°C Flow rate: 0.6ml/min Detector: Differential Refractometer

[Measurement of ²⁹ Si-NMR] Apparatus: AV-500 manufactured by Bruker BioSpin Co., Ltd. ²⁹ Si-NMR resonance frequency: 99.352 MHz Probe: 5 mmφ solution probe Measurement temperature: room temperature (25° C.) Number of sample rotations: 20 kHz Measurement method: reverse Inverse gated decoupling method (Inverse gated decoupling) ²⁹ Si deflection angle: 90∘ ²⁹ Si 90∘ pulse width: 8.0μs repetition time: 5s accumulation times: 9200 observation width: 30kHz

> ²⁹ Si-NMR sample preparation method > In order to shorten the relaxation time, Fe(acac) ₃ as a relaxation reagent was added for measurement. Polysilsesquioxane concentration: 15% Fe(acac) ₃ concentration: 0.6% Determination solvent: acetone Internal standard: TMS

>Waveform Processing Analysis> For each peak of the Fourier-transformed spectrum, the chemical shift is obtained from the position of the peak top and integrated.

[Measurement of Refractive Index] The curable composition was discharged on a horizontal surface, and the refractive index (nD) was measured by pressing the measurement surface of a pen refractometer (manufactured by ATAGO, PEN-RI) at 25°C.

[hardening evaluation] The shear stress was measured with a rheometer (manufactured by Anton Paar, MCR302) using a 20 mm parallel plate, with a test start temperature of 80° C., a heating rate of 5° C./min, a shear strain of 1%, and a frequency of 1 Hz. The temperature at which the shear stress becomes 2000 Pa was defined as the hardening temperature.

[Viscosity evaluation]

Using a rheometer (manufactured by Anton Paar, MCR301), using a cone-plate with a radius of 50 mm and a cone angle of 0.5°, the viscosity at a shear rate of 2 s ⁻¹ and a shear rate of 200 s ⁻¹ at 25° C. was measured. The thixotropic index (viscosity at a shear rate of 2 s ⁻¹ /viscosity at a shear rate of 200 s ⁻¹ ) was obtained from the obtained measured values.

[adhesion strength measurement]

On the mirror surface of a silicon wafer with a side of 2 mm square (area 4 mm ² ), apply the curable composition to a thickness of approximately 2 μm, and press the coated surface on the adherend (silver-plated copper plate) )superior. Thereafter, heat treatment and curing were performed at 170° C. for 2 hours to obtain an adherend with a test piece. Place the adherend with the test piece on the measuring table of the adhesive strength tester (DAGE, Series 4000) preheated to a predetermined temperature (23°C, 100°C) for 30 seconds, at a height of 100 μm from the adherend Near the position, apply stress in the horizontal direction (shear direction) relative to the bonding surface at a speed of 200μm/s, and measure the bonding strength between the test piece and the adherend at 23°C and 100°C respectively (N/4mm ² ).

[Crack resistance evaluation]

On the mirror surface of a glass wafer with a square ( ^0.25mm2 area) of 0.5mm on one side, apply the curable composition to a thickness of about 2μm, and press the coated surface on the adherend (silver-plated copper plate) )superior. Thereafter, heat treatment was performed at 170° C. for 2 hours to harden, and an adherend with a test piece was obtained. Using a digital microscope (VHX-1000, manufactured by Keyence), the resin part (filler part) exuded from the glass wafer was observed, and the number of samples with cracks was counted, and the rate of crack occurrence was rated as "A" from 0% to 25%. More than 25% but less than 50% are evaluated as "B", and 50% or more and 100% are evaluated as "C".

[Peel resistance evaluation]

The curable composition was applied to an LED lead frame (manufactured by Enomoto, 5050 D/G PKG LEADFRAME) at about 0.4 mmφ, and pressed onto a sapphire wafer with a square (area: 0.25 mm ² ) of 0.5 mm on one side. After that, heat treatment at 170°C for 2 hours to harden, pour the sealant (Shin-Etsu Chemical Co., Ltd., LPS-3419) into the cup, heat at 120°C for 1 hour, and then heat at 150°C for 1 hour , to obtain test pieces. This test piece was exposed to an environment of 85°C and 85%RH for 168 hours, preheated at 160°C, and the maximum temperature was 260°C for 1 minute of IR reflow (reflow furnace: manufactured by Sagami Riko Co., Ltd., product name " WL-15-20DNX type") for processing. Afterwards, with the thermal cycle tester, the test of standing at -40°C and +100°C for 30 minutes each was regarded as one cycle, and 500 cycles were implemented. Thereafter, an operation of removing the sealing material was carried out, and it was checked whether or not the elements were peeled off together at this time. This test was performed 100 times for each curable composition. The number of times the components peeled off at the same time was counted, and if the peeling occurrence rate was 25% or less, it was rated as "A", if it was more than 25%, 50% or less, it was rated as "B", and if it was more than 50%, it was rated as "C".

[Table 1] Hardened Peel resistance A A A A A A A A A A Burst resistance A A A A A A A A A A Bonding strength (N/4mm ² ) 100°C 72.5 74.3 66.2 70.9 72.5 85 86 88 90 55.9 23°C 140.2 143.7 135.0 127.4 134.1 115 110 118 136 88.8 hardening composition Viscosity Evaluation [Thixotropic Index] 4.2 3.8 4.3 4.3 4.7 4.5 5.1 4.2 5.1 3.8 hardening [hardening temperature] 186°C 189°C 186°C 191°C 193°C 204°C 203°C 203°C 202°C 200℃ Refractive index 1.425 1.424 1.425 1.424 1.424 1.416 1.421 1.423 1.435 1.423 hardening polysilsesquioxane compound ²⁹ Si-NMR determination Z3 value 70% 73% 71% 71% 71% 84% 84% 83% 83% 79% Z2 value 28% 25% 28% 27% 27% 16% 16% 17% 17% 20% Mass average molecular weight [Mw] 5900 7100 6500 5800 5500 3500 4600 5300 9500 13000 Ratio of monomer containing F atom [introduction amount] 30mol% 30mol% 30mol% 30mol% 30mol% 30mol% 20mol% 10mol% 0mol% 30mol% Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5

The following matters can be seen from Table 1. It can be seen that in the curable polysilsesquioxane compounds (1)-(5) obtained in Examples 1-5, as a result of ²⁹ Si-NMR measurement, the value of Z2 is in the range of 20-40%. In addition, the mass average molecular weights of the curable polysilsesquioxane compounds (1)-(5) are all in the range of 4000-11000. Curable compositions (1) to (5) containing such curable polysilsesquioxane compounds have a low refractive index (nD) and are sufficiently cured at a relatively low temperature. In addition, the cured products of the curable compositions (1) to (5) have high adhesive strength.

On the other hand, Comparisons 1 to 3 are those using the curable polysilsesquioxane compounds [curable polysilsesquioxane compounds (6) to (8)] of Examples 8 to 10 of Patent Document 4, respectively. In the example of Patent Document 4, in order to compensate for the low reactivity of the silane compound having a fluoroalkyl group, a large amount of the acid catalyst is used. Therefore, this method can only obtain hardening polysilsesquioxane compounds with small Z2 values. In addition, the mass average molecular weight of the curable polysilsesquioxane compound decreased due to the increased introduction amount of 3,3,3-trifluoropropyltrimethoxysilane. For these reasons, the curable compositions (6) to (8) of Comparative Examples 1 to 3 are better than the curable compositions (1) to (8) of Examples 1 to 5 in terms of curability and adhesive strength of cured products 5) Worse.

The curable polysilsesquioxane compound (9) obtained in Comparative Example 4 did not have a repeating unit derived from 3,3,3-trifluoropropyltrimethoxysilane. Therefore, the refractive index (nD) of the curable composition (9) becomes a large value. Furthermore, since the curable polysilsesquioxane compound (9) has a small Z2 value, the curability of the curable composition (9) is insufficient.

The curable polysilsesquioxane compound (10) obtained in Comparative Example 5 had an excessively large molecular weight. As a result, the curable composition (10) was inferior to the curable compositions (1) to (5) of Examples 1 to 5 in terms of curability and adhesive strength of cured products.

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Claims (9)

A curable composition characterized in that it contains the following (A) component and (E) component, (A) component: has a repeating unit represented by the following formula (a-1) and the following formula (a- 2) A curable polysilsesquioxane compound having a repeating unit represented by the formula (a-1), wherein the ratio of the repeating unit represented by the formula (a-1) is 25 mol% or more relative to the total repeating units, and the formula ( The ratio of the repeating unit shown in a-2) is more than 0 mol% and 75 mol% or less with respect to all the repeating units, and it is a curable polysilsesquioxane compound that satisfies the following conditions 1 and 2, [Chem. 1 ]R ¹ -D-SiO _3/2 (a-1)[R ¹ is a fluoroalkyl group represented by the composition formula: C _m H _(2m-n+1) F _n ; m represents an integer from 1 to 10, n Represent more than 2, (2m+1) Integers below; D represents the linking group or single bond that R ¹ is bonded to Si, but except alkylene], [Chemical 2] R ² SiO _3/2 (a-2 )[R ² represents an unsubstituted alkyl group with 1 to 10 carbon atoms, or an aryl group with a substituent or an unsubstituted carbon number of 6 to 12], [Condition 1] when determining hardening polysilsesquioxane In ²⁹ Si-NMR of alkane compounds, peaks of 1 or 2 or more are observed in the region of -62ppm to -52ppm [region (2)], and peaks of -52ppm to -45ppm [region (1) )] and at least one of -73ppm to -62ppm [region (3)], 1 or 2 or more peaks are observed, and Z2 derived from the following formula is 20 to 40%,

P1: Integral value in the region (1), P2: Integral value in the region (2), P3: Integral value in the region (3), [Condition 2] Hardening polysilsesquioxane compound The mass average molecular weight (Mw) is 4,000~11,000; (E) component: it is a fine particle with an average primary particle diameter exceeding 0.04 μm and below 8 μm. The curable composition as described in claim 1, wherein, when ^{the 29} Si-NMR of the curable polysilsesquioxane compound is measured, in the region (3), 1 or 2 or more peak, and Z3 derived from the following formula is 60~80%,

The curable composition as described in item 1 of the patent claims, which further contains the following (B) component, (B) component: a silane coupling agent having a nitrogen atom in the molecule. The curable composition described in item 1 of the patent claims, which further contains the following (C) component, (C) component: a silane coupling agent having an acid anhydride structure in the molecule. The curable composition as described in Claim 1, further comprising the following (D) component, (D) component: fine particles with an average primary particle diameter of 5-40 nm. A hardened product obtained by hardening the curable composition described in any one of claims 1 to 5. The hardened product described in item 6 of the scope of the patent application is an optical element fixing material. A method of using the curable composition, which is a method of using the curable composition described in any one of items 1 to 5 of the patent application as an adhesive for optical element fixing materials. A method of using the curable composition, which is a method of using the curable composition described in any one of items 1 to 5 of the patent application as a sealing material for optical element fixing materials.